We describe a method of selective generation and study of polarization moments of up to the highest-rank kappa=2F possible for a quantum state with total angular momentum F. The technique is based on nonlinear magneto-optical rotation with frequency-modulated light. Various polarization moments are distinguished by the periodicity of light-polarization rotation induced by the atoms during Larmor precession and exhibit distinct light-intensity and frequency dependences. We apply the method to study polarization moments of 87Rb atoms contained in a vapor cell with antirelaxation coating. Distinct ultranarrow (1-Hz wide) resonances, corresponding to different multipoles, appear in the magnetic-field dependence of the optical rotation. The use of the highest-multipole resonances supported by a given system has important applications in quantum and nonlinear optics and in magnetometry.